Identifying components in dissolved humic acid that bind organofluorine contaminants using (1)H{(19)F} reverse...

Interactions between dissolved peat humic acid and two structurally dissimilar organofluorine compounds, perfluoro-2-naphthol and perfluoro-octanoic acid, are probed using a novel (1)H{(19)F} Nuclear Magnetic Resonance (NMR) Spectroscopy technique based on the Saturation Transfer Difference (STD) experiment. This technique is used here to show selectively only those regions of the (1)H NMR spectrum of humic acid that arise from chemical constituents interacting with perfluorinated organic compounds. This approach provides a tool for high-resolution analysis of interactions between contaminants and soil organic matter (SOM) directly at the molecular level. Soil organic matter is a chemically heterogeneous mixture, and traditional techniques used to study sorption or binding phenomenon are unable to resolve multiple processes occurring simultaneously at distinct chemical moieties. Here, multiple interaction domains are identified based on known chemical constituents of humic acid, most notably from lignin- and protein-derived material. Specifically, perfluoro-2-naphthol is shown to interact with lignin, protein, and aliphatic material; however, preference is exhibited for lignin-derived domains, while perfluoro-octanoic acid exhibits near exclusive preference for the protein-derived domains of humic acid.